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WO2025136844A1 - Homocystéine et ses dérivés pour la séparation de minéraux de minerais - Google Patents

Homocystéine et ses dérivés pour la séparation de minéraux de minerais Download PDF

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Publication number
WO2025136844A1
WO2025136844A1 PCT/US2024/060284 US2024060284W WO2025136844A1 WO 2025136844 A1 WO2025136844 A1 WO 2025136844A1 US 2024060284 W US2024060284 W US 2024060284W WO 2025136844 A1 WO2025136844 A1 WO 2025136844A1
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depressant
water
heteroatoms
ore
optionally
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Francisco BUITRAGO
Jean-Christophe LEC
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Arkema Inc
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Arkema Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/012—Organic compounds containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/06—Depressants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores

Definitions

  • the invention relates to methods and compositions useful for separation of valuable minerals from ores.
  • Froth flotation is a mineral processing technique used to amass valuable minerals found in low concentrations in ore deposits throughout the earth’s crust.
  • An application of froth flotation is the separation of different valuable minerals from one another taking advantage of different surface interactions with water and air.
  • many reagents are commercially used by mineral processing companies around the world.
  • One class of such reagents is called depressants, which selectively interact with certain minerals to make them hydrophilic and sink (or depress) in the flotation process, while other minerals in the same process remain hydrophobic and float to the top of the flotation cell, typically by associating with, attaching to, and/or being enveloped by bubbles introduced by sparging with a gas.
  • Commercially used depressants especially those used to separate molybdenum from copper, can be toxic to workers and the environment, are typically difficult to remove from water and typically have the disadvantage of emitting hydrogen sulfide gas.
  • 7,776,844 discloses an N-(phosphonoalkyl)-amino acid, a related compound or a derivative thereof, the N-(phosphonoalkyl)-amino acid, related compound or derivative thereof being in a form as a free acid, salt, partial salt, lactone, amide or ester, or in stereoisomeric or non-stereoisomeric form, other than N-(phosphonomethyl)-glycine or N,N- bis(phosphonomethyl)-glycine.
  • U.S. Patent No. 9,511,378 discloses collector compositions including an amidoamine and an amine and methods for making and using same to purify one or more crude materials.
  • Chinese Patent Publication No. CN 113617532 A discloses a combined inhibitor for flotation separation of lead-sulfur sulfide ores and application thereof, in which the combined inhibitor includes L-cysteine and sodium poly naphthalenesulfonate.
  • the inventors have found that homocysteine, metal salts or derivatives thereof, compounds having a structure of Formula (I) below, reaction products thereof with CS2, or combinations thereof as a Cu depressant in inverse Mo aqueous flotation has the potential to reduce and/or eliminate health and environmental issues associated with NaSH and/or H2S, mitigate explosivity risks related to H2S release, and resolve performance issues of alternative depressants (such as limited facility to separate out depressant or in situ reaction products thereof from process water for water recirculation).
  • alternative depressants such as limited facility to separate out depressant or in situ reaction products thereof from process water for water recirculation.
  • a component that is “water insoluble” means that, when the component is combined with water, the resulting mixture has suspended or settled particulates that are visible (and/or 0.2-micron filterable) as a result of the water insoluble component.
  • a component that is “water compatible” indicates that the component is either water soluble or water miscible, such that, when the component is combined with water, the resulting composition has no suspended or settled particulates that are visible (or 0.2-micron filterable) as a result of the water compatible component.
  • the basic and novel characteristics of the claimed composition or method may specifically include separation of at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, or at least 99% of a weight of a desired mineral from an ore, based on the weight of the desired mineral in the ore.
  • a method for separation of minerals in an ore comprises:
  • a slurry comprising: the ore to be separated, a medium (typically comprising water - an aqueous medium), and an effective amount of a depressant comprising: homocysteine, a metal salt or derivative thereof, a compound having structure of Formula (I), a reaction product thereof with CS2, or a combination thereof:
  • a depressant comprising: homocysteine, a metal salt or derivative thereof, a compound having structure of Formula (I), a reaction product thereof with CS2, or a combination thereof:
  • R 1 and R 7 are identical or different and are individually: a hydrogen atom; an aromatic ring optionally comprising one or more heteroatoms; or a nonaromatic, linear, branched or cyclic, saturated or unsaturated, hydrocarbon moiety optionally comprising one or more heteroatoms, or R 1 and R 7 together form an optionally substituted heterocyclic ring structure (such as having from 3 to 18 carbon atoms) and optionally comprising one or more heteroatoms in addition to the nitrogen to which R 1 and R 7 are connected;
  • R 1 and/or R 7 may independently be H or may comprise from 1 to 8, from 1 to 4, or from 1 to 2 carbon atoms.
  • R 3 when R 3 is present and comprises a nonaromatic hydrocarbon moiety (optionally comprising one or more heteroatoms), the moiety can contain from 1 to 20 (e.g, from
  • R 3 may be H or may comprise from 1 to 8, from 1 to 4, or from 1 to 2 carbon atoms.
  • R 4 and R 3 when R 4 and R 3 are present and when R 4 and/or R 5 comprise a nonaromatic hydrocarbon moiety (optionally comprising one or more heteroatoms), the moiety can contain from 1 to 20 (e.g, from 2 to 18, from 3 to 16, from 4 to 15, from 5 to 10, from 1 to 16, from 1 to 12, from 1 to 10, from 1 to 8, from 1 to 6, from 1 to 4, or from 1 to 2) carbon atoms.
  • R 4 and/or R 3 may independently be H or may comprise from 1 to 8, from 1 to 4, or from 1 to 2 carbon atoms.
  • a reducing agent may be introduced prior to the separating step (e.g, before, in tandem with, or after the introduction of the depressant), for example to balance out one or more physico- (and/or electro-) chemical effects of the depressant(s).
  • Non-limiting examples of reducing agents can include hydrazine, urea, sodium sulfide (NazS), hydroxylamine, or a combination thereof.
  • the separation step may be a flotation separation.
  • Froth flotation or flotation, is a process of extracting a metal from low-content ores by a stage of concentration. This stage typically precedes a subsequent treatment comprising the heat treatment (also known as smelting) or the leaching and the refining. This is in particular the case with ores of oxides and/or sulfides of lead, zinc, copper, silver, gold, molybdenum, nickel, cobalt, iron, and metals belonging to the platinum group: platinum, palladium, rhodium, ruthenium, iridium and osmium.
  • Flotation is a method that typically concentrates and separates the valuable components of an ore from either the undesirable components, “gangue,” or a different valuable mineral to produce one or two mineral concentrates that may be fed to pyrometallurgical or hydro- metallurgical operations.
  • the process of froth flotation can start by crushing ore into fine particles to provide separate particles of one or more desirable minerals and the undesirable gangue components, and then frothing or “pulping” the ore particles with a medium such as water (if the medium comprises other components in addition to water, it is aqueous, but the water can stand in for all components of an aqueous medium in the description herein, even if those other non- water components are not specifically mentioned).
  • the aqueous ore particles may be combined with a flotation composition, also referred to as a flotation agent, collector or collector agent, which may also include and/or other appropriate additives.
  • a flotation agent also referred to as a flotation agent, collector or collector agent, which may also include and/or other appropriate additives.
  • flotation agents may selectively render the surfaces of the different types of particles hydrophobic, while the depressants may selectively render the surfaces of other types of particles hydrophilic, based on their individual compositions.
  • the frothing is done by passing a stream of air or inert gas bubbles through the aqueous composition of ore and flotation agent, sometimes called “pulp,” in a flotation cell, such that the gas bubbles associate with, attach to, and/or envelop and thus levitate the nowhydrophobic particles as they rise in the hydrophilic aqueous medium.
  • These levitated particles, associated with, attached to, and/or enveloped by the air bubbles can then collect in a froth layer that flows over the weir of the flotation cell.
  • the undesirable gangue or desirable other mineral(s) may be either unaffected by the flotation agent, or rendered relatively hydrophilic by a depressant such as disclosed herein, compared to the minerals that are floated out and thus settle to the bottom of the flotation cell.
  • froth flotation works by separating certain minerals from gangue and/or from other desirable minerals by exploiting differences in their hydrophobicity and hydrophilicity. Hydrophobicity and/or hydrophilicity differences between valuable minerals and waste gangue can be increased through the use of compounds such as depressants, collectors, frothers/surfactants, and/or wetting agents that affect the various compounds in the crushed ore differently.
  • the adhesion of the bubbles to the mineral s/gangue can be promoted by the action of the flotation agent(s) used.
  • the entrained particles of the metal compounds can then rise to the surface and can be recovered in the form of a foam, also known as flotation concentrate.
  • the gangue particles can be recovered in the lower part of the flotation cell.
  • the flotation concentrate which flows over the weir at the top of the flotation cell has a content of desired metal which is therefore considerably higher than that in the starting ore. This content depends on the initial content in the ore and on the selectivity of the composition of the flotation agent. If a depressant such as that disclosed herein is used, the mineral particles that sink or otherwise phase separate from the ore may be removed and further refined.
  • the flotation concentrates and/or the depressed mineral can then be introduced into the heat treatment (or smelting) stage.
  • This stage can typically involve a furnace at temperatures which may exceed 1500°C.
  • the desired metal can be separated in the molten state from the other substances, in particular from the impurities originating from the gangue of the ore, which may be removed in the form of a slag.
  • Depressants can facilitate the separation of sulfide ores either by depressing gangue minerals and floating, or otherwise phase separating the desired mineral, or by holding down (depressing) the desired mineral while floating or otherwise phase separating the undesirable gangue, or by holding down a desired mineral and allowing another desirable mineral to float, or otherwise phase separating from each other.
  • the method may comprise a step of removing at least a portion (preferably a substantial amount) of depressant from the slurry after the flotation separating step. If more than one depressant is added or present, such as one or more depressants described herein plus an additional depressant, the removed depressant may typically comprise the mixture of depressants including the homocysteine, metal salt or derivative thereof, compound having structure of Formula (I) below, reaction product thereof with CS2, or combination thereof, as well as the additional depressant.
  • the removed depressant may comprise the homocysteine, metal salt or derivative thereof, compound having structure of Formula (I) below, reaction product thereof with CS2, or combination thereof, and not the additional depressant(s).
  • the removed depressant may comprise the additional depressant(s) and not the homocysteine, metal salt or derivative thereof, compound having structure of Formula (I) below, reaction product thereof with CS2, or combination thereof.
  • At least 50 wt% e.g, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt%, at least 85 wt%, at least 90 wt%, at least 95 wt%, at least 98 wt%, at least 99 wt%, or at least 99.9 wt%; and typically up to about 100 wt%) of the depressant(s) to be removed from the slurry, based on a total weight of depressant(s) in the slurry, after the flotation separating step.
  • the removing can comprise converting at least a portion of the depressant into a water-insoluble composition, and removing the water-insoluble composition.
  • the converting of the depressant into a water-insoluble composition may comprise adjusting the pH of the slurry to a range from about 4 to about 9 (e.g., if acidic pH, from about 4 to less than 7, from about 5 to less than 7, from about 5 to about 6 or from about 6 to less than 7; if basic pH, from more than 7 to about 9, from more than 7 to about 8, or from about 8 to about 9; if mild pH and not encompassing the entire range from about 4 to about 9, then from about 5 to about 9, from about 4 to about 8, from about 6 to about 9, from about 5 to about 8, or from about 6 to about 8).
  • the pH may be adjusted to or may be from 4.0 to 9.0, from 4.3 to 9.0, from 4.5 to 9.0, from 4.7 to 9.0, from 5.0 to 9.0, from 5.3 to 9.0, from 5.5 to 9.0, from 5.7 to 9.0, from 6.0 to 9.0, from 6.3 to 9.0, from 6.5 to 9.0, from 6.7 to 9.0, from 7.0 to 9.0, from 7.3 to 9.0, from 7.5 to 9.0, from 7.7 to 9.0, from 8.0 to 9.0, from 8.5 to 9.0, from 4.0 to 8.7, from 4.3 to 8.7, from 4.5 to 8.7, from 4.7 to 8.7, from 5.0 to 8.7, from 5.3 to 8.7, from 5.5 to 8.7, from 5.7 to 8.7, from 6.0 to 8.7, from 6.3 to 8.7, from 6.5 to 8.7, from 6.7 to 8.7, from 7.0 to 8.7, from 7.3 to 8.7, from 7.5 to 8.7, from 7.7 to 8.7, from 8.0
  • a first depressant may comprise homocysteine, a metal salt or derivative thereof, a compound having structure of Formula (I), and/or a reaction product thereof with CS2
  • a second depressant may comprise a depressant different from the first depressant, which is called an “additional depressant” herein
  • the converting step may comprise converting a portion or all of each or any depressant.
  • the converting of the depressant into a water-insoluble composition may comprise introducing an oxidant into the slurry.
  • the oxidant may comprise at least one of an organic peroxide, oxygen, ozone, H2O2, fluorine (F2), chlorine (CI2), bromine (Bn), iodine (I2), nitric acid (HNO3), a nitrate, a nitrite, sulfuric acid (H2SO4), peroxydisulfuric acid (H2S2O8), peroxymonosulfuric acid, (H2SO5), a sulfate, a sulfite, hydrochloric acid (HC1), a hypochlorite, a chlorite, a chlorate, a perchlorate, a permanganate, boric acid (H3BO3), a perborate, nitric oxide (NO), nitrous
  • removing at least a portion of the water-insoluble composition comprises at least one of filtration, centrifugation, and solid/liquid extraction. According to some embodiments, at least 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 99, or 100% by weight of the water-insoluble composition may be removed.
  • the (aqueous) medium typically including or being water
  • the separation step (which may include provision to a separation apparatus).
  • the method may be continuous or semi continuous, or batch or semibatch.
  • the depressant can advantageously include homocysteine (2-amino-4-sulfanylbutanoic acid) or derivatives thereof, in particular L- homocysteine, D-homocysteine, or racemic mixtures of homocysteine.
  • homocysteine (2-amino-4-sulfanylbutanoic acid) or derivatives thereof, in particular L- homocysteine, D-homocysteine, or racemic mixtures of homocysteine.
  • L- homocysteine can be present.
  • the depressant can include a reaction product of homocysteine and CS2, or a metal salt thereof, in particular 2-amino-4- sulfanylsulfanylidenethiobutanoic acid, in which the mercaptan of homocysteine is converted into a hydrogen trithiocarbonate, or an alkali (e.g, lithium, sodium, potassium) or alkaline earth (e.g., calcium, magnesium) metal salt thereof.
  • an alkali e.g, lithium, sodium, potassium
  • alkaline earth e.g., calcium, magnesium
  • Cysteine, homocysteine, the mercaptans of Formula (I), and the reaction products thereof with CS2 are referred to as functionalized mercaptans, because, in addition to the pendant -SH moiety, they also comprise at least one pendant amine moiety, such as -NR'R 7 .
  • n can be from 1 to 3, from 2 to 4, from 2 to 3; advantageously n can include or be 2;
  • R 2 can be -OR 3 , and R 3 can be a hydrogen atom or a saturated hydrocarbon moiety having from 1 to 8 carbon atoms, or from 1 to 4 carbon atoms, optionally comprising a heteroatom; advantageously, n can be a hydrogen atom; and • R l and R 7 can individually be a hydrogen atom or a saturated hydrocarbon moiety having from 1 to 8 carbon atoms, or from 1 to 4 carbon atoms, optionally comprising a heteroatom, advantageously, R 1 and R 7 can both be a hydrogen atom;
  • the metal may comprise an alkali metal or alkaline earth metal; in particular an alkali metal.
  • alkali metals include Na, Li, K, Rb, Cs, Be, Ba, Mg, Sr, and Ca.
  • the metal may advantageously comprise Na, K, Li, Ca, Mg, or mixtures thereof; in particular comprising Na and/or K.
  • the depressant may include one or more additional depressants, aside from the homocysteine, metal salt or derivative thereof, compound having structure of Formula (I), reaction product thereof with CS2, or combination thereof, including those characterized herein specifically as “additional depressants.”
  • compositions and methods disclosed herein may be generically used to separate any of a variety of desired ores and/or minerals out from others, a specific ore to be separated may comprise a Cu-bearing mineral, with the depressant selectively targeted to assist the Cu-bearing mineral(s) to phase separate in the separation step.
  • the phase separation may be to sink, under the action of gravity, or enable phase-based separation by other means, such as by centrifugation.
  • the ore to be separated may comprise both a Cu-bearing mineral and a Mobearing mineral, with the depressant selectively causing the Cu-bearing mineral(s) to phase separate in the separation medium, relative to the Mo-bearing mineral(s).
  • the Cu-bearing mineral may comprise at least one of chalcopyrite (CuFeSi), bornite (Cu5FeS4), covellite (CuS), chalcocite (CU2S), and a combination thereof; in particular comprising chalcopyrite.
  • the Mo-bearing mineral may comprise molybdenite (M0S2).
  • a weight ratio of Cu-bearing mineral(s) to Mo-bearing mineral(s) in the disclosed method(s) can be from about 5:1 to about 100000:1 w/w (e.
  • Non-limiting examples of ores and/or minerals that may be separated using the depressant disclosed herein are those that may include both Cu and Mo. Additionally or alternatively, the ore(s) and/or mineral(s) may comprise Fe. It should be understood that these minerals may include mixtures of minerals, e.g., the Cu may be in one mineral and the Mo may be in another mineral and the present method may be used to separate a mixture of these minerals into a Cu-rich component and an Mo-rich component. Thus, the present method may recover as much Cu and Mo as possible while selectively separating Fe (and other non-metallic minerals such as carbonates, silicates, etc.) and/or Mo in general from all other minerals.
  • the main targets can be Mo and Au when they are present with Cu or Ag, such that valuable streams of Mo, Au, Ag and/or Cu may be recovered.
  • the flotation compositions disclosed herein may be used to separate Cu-Mo and/or Cu-Au and/or Au-Mo and/or Ag-Au ores.
  • ores Non limiting examples of ores that may be separated by use of the present method are sulfide mineral including, among others, chalcopyrite (CuFeSz), bornite (CusFeS ⁇ , covellite (CuS), chalcocite (CuzS) and molybdenite (M0S2).
  • the most common co-existing minerals are chalcopyrite and molybdenite.
  • the relative ratios of these ores may be from 60:40 to 99.999:0.001 by weight (e.g., from 70:30 to 99.999:0.001 by weight, from 80:20 to 99.999:0.001 by weight, from 90:10 to 99.999:0.001 by weight, from 95:5 to 99.999:0.001 by weight, from 99:1 to 99.999:0.001 by weight, from 99.9:0.1 to 99.999:0.001 by weight, from 60:40 to 99.99:0.01 by weight, from 70:30 to 99.99:0.01 by weight, from 80:20 to 99.99:0.01 by weight, from 90:10 to 99.99:0.01 by weight, from 95:5 to 99.99:0.01 by weight, or from 99:1 to 99.99:0.01 by weight).
  • the disclosed depressant(s) comprising homocysteine, a metal salt or derivative thereof, a compound having structure of Formula (I), a reaction product thereof with CS2, or a combination thereof may preferentially react and/or complex with copper contaminant sulfide minerals, thus causing them to sink under this fluence of gravity, or to phase-separate due to the action of a centrifuge for example. Effective amount may be determined based on the degree of separation to be attained and/or by the nature of the selective and comparative metal(s) in the mineral(s) to be separated.
  • the effective amount may be enough depressant to effect a recovery of at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, or at least 99% of a weight of a desired mineral from an ore, based on the weight of the desired mineral in the ore.
  • the amount of the depressant may be selected according to a weight of the relevant mineral(s) in the ore and/or based on other considerations relevant to separation (and/or to medium recycle).
  • the depressant may comprise from 10 g/ton to 100 kg/ton (e.g., from 10 g/ton to 50 kg/ton, from 10 g/ton to 25 kg/ton, from 10 g/ton to 10 kg/ton, from 10 g/ton to 5 kg/ton, from 10 g/ton to 3 kg/ton, from 10 g/ton to 1 kg/ton, from 10 g/ton to 500 g/ton, from 100 g/ton to 100 kg/ton, from 100 g/ton to 50 kg/ton, from 100 g/ton to 25 kg/ton, from 100 g/ton to 10 kg/ton, from 100 g/ton to 5 kg/ton, from 100 g/ton to
  • Non-limiting examples of such other depressants can include, but are not necessarily limited to, sodium hydrosulfide (NaSH), Nokes reagent (a reaction product of NaOH and phosphorous pentasulfide), sodium thioglycolate, carboxymethyl cellulose, and disodium carboxymethyl trithiocarbonate (such as commercially available under the tradename Orfom® D8 from Chevron Phillips Chemical), lime (calcium oxide and/or calcium hydroxide), sodium cyanide, zinc sulfate, and combinations thereof.
  • NaSH sodium hydrosulfide
  • Nokes reagent a reaction product of NaOH and phosphorous pentasulfide
  • sodium thioglycolate carboxymethyl cellulose
  • disodium carboxymethyl trithiocarbonate such as commercially available under the tradename Orfom® D8 from Chevron Phillips Chemical
  • lime calcium oxide and/or calcium hydroxide
  • sodium cyanide sodium cyanide
  • zinc sulfate and combinations
  • the collector may further comprise, consist of, or consist essentially of at least one C6-C12 branched or straight chained alkane(s) and/or at least one branched or straight chained C6-C14 alkene, particularly dodecane, dodecene, and/or tetradecene.
  • sulfide (c) having a structure R u -S-R 12 , where R 11 and R 12 are independently selected from C1-C16, or C1-C14, or C1-C12, particularly C1-C10 straight chain and branched alkyl groups, wherein an average number of carbons in the (c) sulfide is from 10-
  • Embodiment 1 A method for separation of minerals in an ore, comprising: introducing into a separation apparatus a slurry comprising: the ore to be separated, water, and an effective amount of a depressant comprising: homocysteine or a metal salt or derivative thereof, a compound having structure of Formula (I), a reaction product thereof with CS2, or a combination thereof: Formula (I) where C* is a chiral carbon and where: R 1 and R 7 are identical or different and are individually: a hydrogen atom; an aromatic ring optionally comprising one or more heteroatoms; or a nonaromatic, linear, branched or cyclic, saturated or unsaturated, hydrocarbon moiety having 1 to 12 carbon atoms and optionally comprising one or more heteroatoms, or R 1 and R 7 together form an optionally substituted heterocyclic ring structure having from 3 to 18 carbon atoms and optionally comprising one or more heteroatoms in addition to the nitrogen to which R 1 and R 7 are connected; X is
  • Embodiment 3 The method of embodiment 1 or embodiment 2, wherein the separating step comprises sparging the slurry with a gas.
  • Embodiment 4 The method of any of embodiments 1-3, wherein the metal comprises an alkaline metal or alkaline earth metal.
  • Embodiment 5 The method of embodiments 1-4, further comprising introducing a reducing agent prior to the separating step.
  • Embodiment 6 The method of embodiment 5, wherein the reducing agent comprises hydrazine, urea, NazS, hydroxylamine, or a combination thereof.
  • Embodiment 7 The method of any of embodiments 1-6, further comprising removing at least a portion of the depressant or the metal salt or derivative thereof from the slurry after the separating step.
  • Embodiment 8 The method of embodiment 7, wherein the removing comprises converting at least a portion of the depressant or the water compatible metal salt or derivative thereof into a water-insoluble composition, and separating out at least a portion of the waterinsoluble composition.
  • Embodiment 9 The method of embodiment 7 or embodiment 8, wherein after the removing, at least a portion of the water is recirculated to the separation apparatus.
  • Embodiment 10 The method of embodiment 8 or embodiment 9, wherein the converting of the depressant or the water compatible metal salt or derivative thereof into a waterinsoluble composition comprises adjusting a pH of the slurry to from about 4 to about 9.
  • Embodiment 11 The method of any of embodiments 8-10, wherein the converting of the depressant or the water compatible metal salt or derivative thereof into a water-insoluble composition comprises introducing an oxidant into the slurry.
  • Embodiment 12 The method of embodiment 11, wherein the oxidant comprises at least one of an organic peroxide, oxygen, ozone, H2O2, fluorine (F2), chlorine (CI2), bromine (Br2), iodine (I2), nitric acid (HNO3), a nitrate, a nitrite, sulfuric acid (H2SO4), peroxy disulfuric acid (H S2O8), peroxymono sulfuric acid, (H2SO5), a sulfate, a sulfite, hydrochloric acid (HC1), a hypochlorite, a chlorite, a chlorate, a perchlorate, a permanganate, boric acid (H3BO3), a perborate, nitric oxide (NO), nitrous oxide (N2O), and combinations and reaction products thereof, in particular comprising H2O2.
  • fluorine F2
  • chlorine chlorine
  • bromine (Br2) bromine
  • Embodiment 13 The method of any of embodiments 7-12, wherein removing the water-insoluble composition comprises at least one of filtration, centrifugation, and solid/liquid extraction.
  • Embodiment 14 The method of any of embodiments 1-13, wherein the depressant comprises homocysteine, an alkali metal or alkaline earth metal salt thereof, a reaction product thereof with CS2, or a combination thereof.
  • Embodiment 15 The method of any of embodiments 1-14, further comprising collecting one or more of the plurality of minerals from the separation step.
  • Embodiment 16 The method of any of embodiments 1-15, wherein the ore to be separated comprises a Cu-bearing mineral, and the depressant selectively causes the Cu-bearing mineral to phase separate in the separation apparatus.
  • Embodiment 17 The method of any of embodiments 1-16, wherein the ore to be separated comprises a Cu-bearing mineral and a Mo-bearing mineral, and the depressant selectively causes the Cu-bearing mineral to phase separate in the separation apparatus relative to the Mo-bearing mineral.
  • Embodiment 18 The method of embodiment 16 or embodiment 17, wherein, the Cubearing mineral comprises at least one of chalcopyrite (CuFeS2), bornite (CusFeS ⁇ , covellite (CuS), chalcocite (C112S), and a combination thereof; in particular comprises chalcopyrite.
  • the Cubearing mineral comprises at least one of chalcopyrite (CuFeS2), bornite (CusFeS ⁇ , covellite (CuS), chalcocite (C112S), and a combination thereof; in particular comprises chalcopyrite.
  • Embodiment 19 The method of embodiment 17 or embodiment 18, wherein the Mobearing mineral comprises molybdenite (M0S2).
  • Embodiment 20 The method of any of embodiments 1-19, wherein the method is continuous or semi-continuous or batch or semibatch.
  • NDM represents a commercial n-dodecyl mercaptan product. Although the “dodecyl” descriptor seems to indicate only C12 linear primary thiols, it should be understood that the commercial product typically comprises a range of carbon numbers with 12 as the predominant or target number of carbons and that the commercial product may contain some level of branched primary thiols and perhaps even secondary thiols.
  • Example 1
  • Table 1 Composition of Mineral 1 as determined by X-ray diffraction.
  • a Mineral 1 sample containing particle sizes between -75-150 microns was added to water to make a slurry containing approximately 1% solids by weight.
  • the slurry pH was modified by NaOH or HC1 addition before adding L-homocysteine (-100 microliters of -8.2 wt% aqueous solution) and NDM (-4 microliters neat).
  • Methyl isobutyl carbinol (MIBC) was added as a frother (-2 microliters neat) before bubbling N2 gas or air through the slurry at -40 mL/minute. The gas caused the hydrophobic particles to float to the surface to be collected as a concentrate, while the hydrophilic particles remained in the bottom of the Hallimond tube.
  • NDM can act as a collector for Mineral 1 , leading to recoveries of -70-80% at pH values between about 4 and about 12.
  • Figure 1 shows that the experiments without NDM as collector resulted in minimal chalcopyrite recovery.
  • the dosages of L-HCY, DL-HCY and DL- CYS were -40 micromol per 2 grams of Mineral 1.
  • the dosages for 2Na-HCY and 2Na-MEPZD were ⁇ 60 micromol per 2 grams of Mineral 1. It is worth noting that MEPZD alone was not sufficiently soluble in water and was converted to a salt in order to allow enough solubility for the experiments. The results are shown in Figure 3.
  • L-HCY L-homocysteine
  • Table 2 Cu, Mo and Fe recovery using NaSH and L-HCY as depressants.
  • Examples 4a-4h [0101] Pure L-homocysteine (L-HCY) was soluble in water up to ⁇ 10 wt%. However, solids can precipitate in a few hours. On the other hand, depressant formulation stability for mining can be improved by converting L-HCY into its alkaline salts. For example, the disodium salt of L- HCY (2Na-HCY) was soluble in water up to ⁇ 35 wt%. A similar ⁇ 23 wt% 2Na-HCY sample (Example 4e) exhibited consistent shelf-life for at least ⁇ 2 years.
  • L-HCY L-cysteine
  • methionine methionine
  • This concentration represents too low of an active ingredient content to make its use as a commercial depressant practical.

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  • Manufacture And Refinement Of Metals (AREA)

Abstract

L'invention concerne un procédé de séparation de minéraux dans un minerai. Le procédé consiste à : introduire dans un appareil de séparation une suspension comprenant le minerai à séparer, de l'eau et une quantité efficace d'homocystéine ou d'un sel métallique ou d'un dérivé de celle-ci, un composé ayant une structure de formule (I), un produit de réaction de celui-ci avec CS2, ou une combinaison de ceux-ci : NR1R7-CH(XR2)((CH2)nSH) (I) ; et séparer tout ou partie du minerai en une pluralité de minéraux.
PCT/US2024/060284 2023-12-18 2024-12-16 Homocystéine et ses dérivés pour la séparation de minéraux de minerais Pending WO2025136844A1 (fr)

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